JP3316048B2 - Building material and manufacturing method thereof - Google Patents
Building material and manufacturing method thereofInfo
- Publication number
- JP3316048B2 JP3316048B2 JP23956393A JP23956393A JP3316048B2 JP 3316048 B2 JP3316048 B2 JP 3316048B2 JP 23956393 A JP23956393 A JP 23956393A JP 23956393 A JP23956393 A JP 23956393A JP 3316048 B2 JP3316048 B2 JP 3316048B2
- Authority
- JP
- Japan
- Prior art keywords
- metal
- mixture
- building material
- oxide
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000004566 building material Substances 0.000 title claims description 44
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 161
- 239000002184 metal Substances 0.000 claims description 161
- 239000000203 mixture Substances 0.000 claims description 48
- 150000004706 metal oxides Chemical class 0.000 claims description 45
- 229910044991 metal oxide Inorganic materials 0.000 claims description 43
- 230000001699 photocatalysis Effects 0.000 claims description 35
- 229910052763 palladium Inorganic materials 0.000 claims description 19
- 229910052709 silver Inorganic materials 0.000 claims description 18
- 229910052719 titanium Inorganic materials 0.000 claims description 18
- 229910052759 nickel Inorganic materials 0.000 claims description 17
- 229910052697 platinum Inorganic materials 0.000 claims description 17
- 229910052802 copper Inorganic materials 0.000 claims description 16
- 229910052737 gold Inorganic materials 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 11
- 238000012545 processing Methods 0.000 claims description 10
- 229910052725 zinc Inorganic materials 0.000 claims description 10
- 238000009751 slip forming Methods 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 230000001747 exhibiting effect Effects 0.000 claims description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 239000000956 alloy Substances 0.000 description 27
- 229910045601 alloy Inorganic materials 0.000 description 27
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 22
- 239000010936 titanium Substances 0.000 description 22
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 19
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- 230000000844 anti-bacterial effect Effects 0.000 description 13
- 239000002781 deodorant agent Substances 0.000 description 12
- 230000000843 anti-fungal effect Effects 0.000 description 11
- 229940121375 antifungal agent Drugs 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 239000010408 film Substances 0.000 description 9
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 239000010931 gold Substances 0.000 description 8
- 239000010944 silver (metal) Substances 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 229910002056 binary alloy Inorganic materials 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000007743 anodising Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000855 fungicidal effect Effects 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000004332 deodorization Methods 0.000 description 4
- 230000001877 deodorizing effect Effects 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 239000000417 fungicide Substances 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 238000013032 photocatalytic reaction Methods 0.000 description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- MZFIXCCGFYSQSS-UHFFFAOYSA-N silver titanium Chemical compound [Ti].[Ag] MZFIXCCGFYSQSS-UHFFFAOYSA-N 0.000 description 3
- 238000004528 spin coating Methods 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910001923 silver oxide Inorganic materials 0.000 description 2
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 239000003429 antifungal agent Substances 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000002538 fungal effect Effects 0.000 description 1
- 230000002070 germicidal effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Panels For Use In Building Construction (AREA)
- Catalysts (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、建築材料及びその製造
方法に関し、詳しくは、表面に高光触媒機能を有し、防
臭・防黴・防菌作用のある金属性建築材料及びその製造
方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a building material and a method for producing the same, and more particularly, to a metal building material having a surface having a high photocatalytic function and having an odor-proofing, a mold-proofing and a bacteriostatic action, and a method for producing the same. .
【０００２】[0002]
【従来の技術】酸化チタン等の半導体は、特定の波長の
光により光触媒機能を発現し、強力な酸化作用により防
臭・防黴・防菌機能を有することが知られている。防菌
防黴誌、第１３巻第５号第２１１頁（１９８５年）に
は、酸化チタン微粒子固定膜が殺菌リアクターとして有
用である点が記載され、特公平２−９８５０号には、酸
化チタン等の半導体に金属または金属酸化物を担持した
ものを用いた廃棄物の浄化方法が記載されている。2. Description of the Related Art It is known that a semiconductor such as titanium oxide exhibits a photocatalytic function by light of a specific wavelength, and has a deodorant, antifungal and antibacterial functions due to a strong oxidizing action. No. 13, No. 5, p. 211 (1985) describes that a titanium oxide fine particle fixed membrane is useful as a sterilization reactor. A method for purifying waste using a semiconductor or the like carrying a metal or a metal oxide is described.
【０００３】従来、光触媒として、半導体機能を有する
酸化チタン、酸化鉄、酸化タングステン、酸化ケイ素等
もしくはそれらに触媒機能を向上させる目的で白金の如
き金属を担持させたものを用いており、防臭・防黴・防
菌機能を利用するために、それを微粒子化して表面に固
定膜を形成させたり、該微粒子を処理する目的物に分散
させたりして用いていた。Conventionally, photocatalysts such as titanium oxide, iron oxide, tungsten oxide, silicon oxide, and the like having a semiconductor function, or those carrying a metal such as platinum for the purpose of improving the catalytic function have been used. In order to utilize the fungicidal and antibacterial functions, they have been used in the form of fine particles to form a fixed film on the surface, or the fine particles are dispersed in a target substance to be treated.
【０００４】該光触媒機能を利用して、建築材料に防臭
・防黴・防菌機能を付与するために、微粒子化した光触
媒を建築材料に塗布する方法として、スプレー法、ディ
ップコーティング法、スピンコーティング法が知られて
いる。しかしながら、微粒子分散物を塗布した皮膜は、
ミクロ的にみると均一性に欠けており、このため、光触
媒機能の効率が悪く、膜強度も不足しており、建築材料
に対する付着強度も充分ではないため耐剥離性に乏し
く、清掃時等に傷ついたり、剥がれたりする問題があっ
た。また、これら半導体材料を薄膜化して、材料に接着
することも提案されたが、薄膜化技術が困難であり、薄
膜化工程での酸処理、アルカリ処理による建築材料への
悪影響が懸念されるため、未だ実用化には至っていな
い。[0004] In order to impart a deodorant / antifungal / antibacterial function to building materials using the photocatalytic function, spraying, dip coating, spin coating, and the like can be applied to building materials. The law is known. However, the film coated with the fine particle dispersion is
Microscopically, it lacks uniformity, so the efficiency of the photocatalytic function is poor, the film strength is also insufficient, and the adhesion strength to building materials is not enough, so it has poor peeling resistance, and There was a problem of being hurt or peeling. It has also been proposed that these semiconductor materials be thinned and adhered to the material, but because thinning technology is difficult, acid treatment and alkali treatment in the thinning process may adversely affect building materials. Has not yet been put to practical use.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、材料
の均一性が高く、防臭・防黴・防菌機能に優れ、さらに
製造が簡便であり、かつ、強度があって、耐久性に優
れ、しかも、目的に応じた形状への加工が容易な建築材
料を提供することにある。本発明の第２の目的は、均一
で、耐久性、防臭・防黴・防菌効果に優れた建築材料の
簡便な製造方法を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a material having high uniformity, excellent deodorant, antifungal, and antibacterial functions, simple production, high strength, and high durability. An object of the present invention is to provide a building material which is excellent and can be easily processed into a shape according to the purpose. A second object of the present invention is to provide a simple method for producing a building material which is uniform and excellent in durability, odor-proofing, mold-proofing and germicidal effects.
【０００６】[0006]
【課題を解決するための手段】本出願に係わる請求項１
記載の発明は、建築材料であって、表面及びその近傍が
実質的に光触媒活性を示すＴｉＯ 2 又はＺｎＯである金
属酸化物及び該金属酸化物の光触媒活性を向上させる機
能を有するＰｔ、Ａｕ、Ｐｄ、Ａｇ、Ｃｕ、Ｎｉ、Ｃｏ
からなる群より選択される第二の金属を含有する金属混
合体からなり、内部が実質的に該金属酸化物を構成する
ものと同種の金属であるＴｉ又はＺｎ及び該金属酸化物
の光触媒活性を向上させる該第二の金属を含有する金属
混合体からなり、該表面及びその近傍と内部が連続的に
構成されていることを特徴とする。Means for Solving the Problems Claim 1 according to the present application
The invention described is a building material, machine to improve the photocatalytic activity of the surface and the gold <br/> genus oxide and the metal oxide near is TiO 2 or ZnO exhibit substantially photocatalytic activity
Pt, Au, Pd, Ag, Cu, Ni, Co
Consisting of a metal mixture containing a second metal selected from the group consisting of Ti or Zn , the inside of which is substantially the same metal as that constituting the metal oxide, and the photocatalytic activity of the metal oxide And a metal mixture containing the second metal for improving the surface roughness, wherein the surface, its vicinity and the inside are continuously formed.
【０００７】本出願に係わる請求項２記載の発明は、請
求項１記載の建築材料であって、表面及びその近傍が実
質的に一般式（Ｉ）で表される金属混合体からなり、According to a second aspect of the present invention, there is provided a building material according to the first aspect, wherein the surface and the vicinity thereof are substantially composed of a metal mixture represented by the general formula (I),
【０００８】［化４］ 一般式（Ｉ） 〔ＡＯz 〕X 〔ＡＭy 〕1-X 又は〔ＡＯz 〕X Ｍ1-X （式中、ＡはＴｉ又はＺｎを表し、ＭはＰｔ、Ａｕ、Ｐ
ｄ、Ａｇ、Ｃｕ、Ｎｉ、Ｃｏからなる群より選択される
金属を表し、ｚは金属Ａと結合する酸素原子の比であっ
て、ｚ≦２を表し、ｘは０．３≦ｘ＜１、ｙは金属Ａと
結合する金属Ｍ固有の整数であって、ｙ＝１、２、３の
いずれかを表す。） 内部が実質的に一般式（ＩＩ）で表される金属混合体か
らなっており、[0008] [Chemical formula 4] In the general formula (I) [AO z] X [AM y] 1-X or [AO z] X M 1-X (wherein, A represents Ti or Zn, M is Pt, Au, P
represents a metal selected from the group consisting of d, Ag, Cu, Ni, and Co, z is a ratio of oxygen atoms bonded to the metal A, and represents z ≦ 2, and x is 0.3 ≦ x <1 , Y is an integer unique to the metal M bonded to the metal A, and represents one of y = 1, 2, and 3. The inside is substantially composed of a metal mixture represented by the general formula (II),
【０００９】［化５］ 一般式（ＩＩ） 〔Ａ〕X 〔ＡＭy 〕1-X 又は〔Ａ〕X Ｍ1-X （式中、ＡはＴｉ又はＺｎを表し、ＭはＰｔ、Ａｕ、Ｐ
ｄ、Ａｇ、Ｃｕ、Ｎｉ、Ｃｏからなる群より選択される
金属を表し、ｘは０．３≦ｘ＜１、ｙは金属Ａと結合す
る金属Ｍ固有の整数であって、ｙ＝１、２、３のいずれ
かを表す。） 表面及びその近傍と内部が連続的に構成されていること
を特徴とするものである。[Chemical Formula 5] [A] X [AM y ] 1-X or [A] X M 1-X (where A represents Ti or Zn , M represents Pt, Au, P
represents a metal selected from the group consisting of d, Ag, Cu, Ni, and Co, where x is 0.3 ≦ x <1, y is an integer specific to metal M bonded to metal A, and y = 1, Represents any of 2 and 3. The present invention is characterized in that the surface, its vicinity and the inside are continuously formed.
【００１０】本出願に係わる請求項４記載の発明は、前
記の建築材料の製造方法であって、光触媒活性を示す金
属酸化物を生成せしめる金属であるＴｉ又はＺｎ及び金
属酸化物の光触媒活性を向上させる機能を有するＰｔ、
Ａｕ、Ｐｄ、Ａｇ、Ｃｕ、Ｎｉ、Ｃｏからなる群より選
択される第二の金属を含有する金属混合体を製造し、該
金属混合体を所望の形状に加工したのち、該金属混合体
を加工したものを酸化処理して表面に光触媒相を形成す
ることを特徴とする。According to a fourth aspect of the present invention, there is provided the method for producing a building material, wherein Ti or Zn, which is a metal for generating a metal oxide having photocatalytic activity, and the photocatalytic activity of the metal oxide are used. Pt having a function to improve ,
Selected from the group consisting of Au, Pd, Ag, Cu, Ni, Co
A metal mixture containing the selected second metal is produced, the metal mixture is processed into a desired shape, and the processed metal mixture is oxidized to form a photocatalytic phase on the surface . <br/>
【００１１】本出願に係わる請求項５記載の発明は、請
求項４記載の建築材料の製造方法であって、一般式（Ｉ
Ｉ）で表される金属混合体を製造し、According to a fifth aspect of the present invention, there is provided a method for producing a building material according to the fourth aspect , wherein the general formula (I)
Producing a metal mixture represented by I),
【００１２】［化６］ 一般式（ＩＩ） 〔Ａ〕X 〔ＡＭy 〕1-X 又は〔Ａ〕X Ｍ1-X （式中、ＡはＴｉ又はＺｎを表し、ＭはＰｔ、Ａｕ、Ｐ
ｄ、Ａｇ、Ｃｕ、Ｎｉ、Ｃｏからなる群より選択される
金属を表し、ｘは０．３≦ｘ＜１、ｙは金属Ａと結合す
る金属Ｍ固有の整数であって、ｙ＝１、２、３のいずれ
かを表す。） 該金属混合体を所望の形状に加工したのち、該金属混合
体を加工したものを酸化処理して表面に光触媒相を形成
することを特徴とするものである。[Chemical formula 6] [A] X [AM y ] 1 -X or [A] X M 1 -X (where A represents Ti or Zn , M represents Pt, Au, P
represents a metal selected from the group consisting of d, Ag, Cu, Ni, and Co, where x is 0.3 ≦ x <1, y is an integer specific to metal M bonded to metal A, and y = 1, Represents any of 2 and 3. After processing the metal mixture into a desired shape, the processed metal mixture is oxidized to form a photocatalytic phase on the surface .
【００１３】[0013]
【作用】本発明の建築材料は、表面及びその近傍に酸化
チタン等の光触媒機能を有する金属酸化物と該金属酸化
物の触媒機能を向上させる金属との混合体を用い、内部
にチタン等前記金属酸化物を構成する金属単体と前記触
媒機能を向上させる金属との金属混合体を用いて連続的
に構成されているため、表面に均一な光触媒相が形成さ
れ、効率的な光触媒反応によって優れた防臭・防黴・防
菌効果を発現する。また、光触媒相がリジッドに、か
つ、連続的に形成されているため触媒相の剥離がなく、
加工も容易である。また、チタン等の、金属酸化物を生
成することができる金属単体と前記触媒機能を向上させ
る金属の金属混合体（合金）を成型加工したのち、酸化
処理することにより、表面に光触媒機能を有する相が形
成された建築材料を製造するため、防臭・防黴・防菌効
果に優れ、均一で任意の形状の建築材料が、簡便な方法
により得られる。The building material of the present invention uses a mixture of a metal oxide having a photocatalytic function, such as titanium oxide, on the surface and in the vicinity thereof and a metal for improving the catalytic function of the metal oxide. Since the metal oxide is continuously formed by using a metal mixture of a simple metal and a metal that improves the catalytic function, a uniform photocatalytic phase is formed on the surface, and excellent by an efficient photocatalytic reaction. It has a deodorant, antifungal and antibacterial effect. In addition, since the photocatalyst phase is rigid and formed continuously, there is no separation of the catalyst phase,
Processing is easy. In addition, after molding a metal mixture (alloy) of a simple metal, such as titanium, capable of producing a metal oxide and the metal for improving the catalytic function, the surface is provided with a photocatalytic function by an oxidation treatment. Since a building material having a phase formed therein is produced, a building material having an excellent deodorizing, antifungal and antibacterial effect and having a uniform and arbitrary shape can be obtained by a simple method.
【００１４】[0014]
【実施例】以下、本発明を更に詳しく説明する。The present invention will be described in more detail below.
【００１５】本発明の建築材料は、表面及びその近傍が
実質的に光触媒活性を示す金属酸化物及び該金属酸化物
の光触媒活性を向上させる第二の金属を含有する金属混
合体からなり、内部が実質的に該金属酸化物を構成する
ものと同種の金属及び該金属酸化物の光触媒活性を向上
させる第二の金属を含有する金属混合体からなり、該表
面及びその近傍と内部が連続的に構成されていることを
特徴とするものであり、特に、好ましい一般式により示
せば、表面及びその近傍が実質的に下記一般式（Ｉ）で
表される金属混合体からなり、[0015] The building material of the present invention comprises a metal mixture containing a metal oxide having a photocatalytic activity substantially at the surface and the vicinity thereof and a second metal for improving the photocatalytic activity of the metal oxide, Consists essentially of a metal mixture containing the same kind of metal as the metal oxide and a second metal that improves the photocatalytic activity of the metal oxide, wherein the surface and its vicinity and the interior are continuous. In particular, if shown by a preferred general formula, the surface and its vicinity substantially consist of a metal mixture represented by the following general formula (I),
【００１６】[0016]
【化７】一般式（Ｉ） 〔ＡＯz 〕X 〔ＡＭy 〕1-X 又は〔ＡＯz 〕X Ｍ1-X （式中、ＭはＰｔ、Ａｕ、Ｐｄ、Ａｇ、Ｃｕ、Ｎｉ、Ｃ
ｏからなる群より選択される金属を表し、ｘは０．３≦
ｘ＜１、ｙはＡと結合する金属Ｍ固有の整数であって、
ｙ＝１、２、３のいずれかを表す。） 内部が実質的に一般式（ＩＩ）で表される金属混合体か
らなっており、Embedded image In the general formula (I) [AO z] X [AM y] 1-X or [AO z] X M 1-X (wherein, M is Pt, Au, Pd, Ag, Cu, Ni, C
x represents a metal selected from the group consisting of
x <1, y is an integer specific to metal M bonded to A,
y represents one of 1, 2, and 3. The inside is substantially composed of a metal mixture represented by the general formula (II),
【００１７】[0017]
【化８】一般式（ＩＩ） 〔Ａ〕X 〔ＡＭy 〕1-X 又は〔Ａ〕X Ｍ1-X （式中、ＭはＰｔ、Ａｕ、Ｐｄ、Ａｇ、Ｃｕ、Ｎｉ、Ｃ
ｏからなる群より選択される金属を表し、ｘは０．３≦
ｘ＜１、ｙはＡと結合する金属Ｍ固有の整数であって、
ｙ＝１、２、３のいずれかを表す。） 表面及びその近傍と内部が連続的に構成されている。各
々の割合としては、表面に近い部分ほど、金属酸化物
〔ＡＯz 〕の含有量が多く、内部では、金属単体〔Ａ〕
の割合が多くなる。Formula (II) [A] X [AM y ] 1-X or [A] X M 1-X (where M is Pt, Au, Pd, Ag, Cu, Ni, C
x represents a metal selected from the group consisting of
x <1, y is an integer specific to metal M bonded to A,
y represents one of 1, 2, and 3. ) The surface, its vicinity and the inside are continuously formed. As for the respective proportions, the closer to the surface, the higher the content of the metal oxide [AO z ], and inside the metal element [A]
Ratio increases.
【００１８】ｚは金属Ａと結合する酸素原子〔Ｏ〕のモ
ル比を表し、ｚ≦２である。ｘは金属混合体中の金属酸
化物〔ＡＯz 〕或いは金属〔Ａ〕と、触媒機能を向上さ
せるための金属〔Ｍ〕との割合を示すモル比を表してお
り、ｘの値は０．３以上１未満であることを要し、０．
７〜０．９程度が好ましい。Z represents the molar ratio of the oxygen atom [O] bonded to the metal A, and z ≦ 2. x represents a molar ratio indicating the ratio of the metal oxide [AO z ] or the metal [A] in the metal mixture to the metal [M] for improving the catalytic function, and the value of x is 0.1. It must be 3 or more and less than 1.
About 7 to 0.9 is preferable.
【００１９】本発明において、光触媒機能を発現する物
質として用いうるものとしては、通常、光触媒機能を発
現する半導体として知られている、特公平２−９８５０
号の記載の如き物質が挙げられ、具体例としては、酸化
チタン、酸化鉄、酸化銀、酸化銅、酸化タングステン、
酸化アルミニウム、酸化亜鉛、酸化珪素、チタン酸スト
ロンチウム等が挙げられ、本発明の建築材料に使用する
金属酸化物としてはこれら半導体をすべて包含するもの
である。これら金属酸化物のなかでも、防臭・防黴・防
菌効果の観点から、前記一般式（Ｉ）で表される酸化チ
タン、酸化鉄、酸化銀、酸化銅、酸化亜鉛等が好まし
く、その他の物質としてはチタン酸ストロンチウムが好
ましく用いられる。加工の容易性、価格の点から、特に
酸化チタンが好ましく用いられる。In the present invention, a substance which can be used as a substance exhibiting a photocatalytic function is generally known as a semiconductor exhibiting a photocatalytic function, which is disclosed in Japanese Patent Publication No. 2-9850.
Examples of such substances include titanium oxide, iron oxide, silver oxide, copper oxide, tungsten oxide, and the like.
Examples thereof include aluminum oxide, zinc oxide, silicon oxide, and strontium titanate. The metal oxide used in the building material of the present invention includes all of these semiconductors. Among these metal oxides, titanium oxide, iron oxide, silver oxide, copper oxide, zinc oxide, and the like represented by the general formula (I) are preferable from the viewpoint of deodorant, fungicide, and antibacterial effects. Strontium titanate is preferably used as the substance. Titanium oxide is particularly preferably used in terms of ease of processing and cost.
【００２０】前記金属酸化物の光触媒活性を向上させる
第二の金属は、金属酸化物と共存して、光触媒反応にお
いて還元反応サイトになりうる金属で、一般には、貴金
属と呼ばれるものであり、周期律表VIII族Ｉ族ｂの元素
などが代表的に挙げられる。本発明においては、前記一
般式（Ｉ）で表される金属酸化物〔ＡＯz 〕の触媒機能
を向上させるための金属Ｍとして、効果の高い白金、
金、パラジウム、銀、銅、ニッケル、コバルトが好まし
く例示されている。これらのうち、防臭・防黴・防菌効
果の点から白金、金、パラジウム、銀が好ましく、加工
の容易さ、価格の点からパラジウムが特に好ましい。The second metal for improving the photocatalytic activity of the metal oxide is a metal which can coexist with the metal oxide and serve as a reduction reaction site in a photocatalytic reaction, and is generally called a noble metal. Typical examples include elements of Group VIII of Group VIII and Group b. In the present invention, highly effective platinum is used as the metal M for improving the catalytic function of the metal oxide [AO z ] represented by the general formula (I).
Gold, palladium, silver, copper, nickel and cobalt are preferably exemplified. Of these, platinum, gold, palladium, and silver are preferred from the viewpoint of deodorant, fungicide, and antibacterial effects, and palladium is particularly preferred from the viewpoint of ease of processing and price.
【００２１】本発明において、実質的とは、本発明の効
果を損なわない程度の不純物、混合物の存在を包含する
意味を有するものである。In the present invention, “substantially” has a meaning that includes the presence of impurities and mixtures that do not impair the effects of the present invention.
【００２２】ここで、本発明の建築材料の組織を、前記
一般式（Ｉ）、一般式（ＩＩ）によって説明するに、表
面及びその近傍では、金属酸化物〔ＡＯz 〕とＭなる群
から選択される金属とは、混合により合金と類似の組織
を呈する。すなわち、（ａ）金属酸化物〔ＡＯz 〕のみ
からなる相と金属酸化物と金属Ｍとの複合体相〔Ａ
Ｍ y 〕とが微細かつ均一に分散した混合組織（金属混合
体）｛〔ＡＯZ 〕X 〔ＡＭ y 〕1-X ｝、もしくは（ｂ）
金属酸化物〔ＡＯz 〕のみからなる相と金属Ｍとが微細
かつ均一に分散した金属混合体｛〔ＡＯZ 〕X Ｍ1-X ｝
を呈するものである。これらは、内部にいくにしたがっ
て、金属混合体中の金属酸化物〔ＡＯz 〕が金属Ａにお
きかわって、金属酸化物〔ＡＯz 〕と金属Ｍとの金属混
合体（合金）に連続的に変化していく。このとき、金属
Ａとしては、防臭・防黴・防菌効果及び加工性、入手の
容易さから、チタンが好ましく用いられる。Here, the structure of the building material of the present invention is
Tables explaining the general formulas (I) and (II)
Metal oxide [AO]z] And M
The metal selected from is a structure similar to an alloy by mixing
Present. That is, (a) a metal oxide [AOz〕only
Composite phase of a phase composed of a metal oxide and a metal M [A
M y] And a finely and uniformly dispersed mixed structure (metal mixture
Body) ｛[AOZ]X[AM y]1-X｝ Or (b)
Metal oxide [AOz] And the metal M are fine
And uniformly dispersed metal mixture {[AOZ]XM1-X｝
It shows. These are going inside
Metal oxide [AO]z] On metal A
On the other hand, metal oxide [AOz] And metal M
It continuously changes to coalescence (alloy). At this time, metal
As A, deodorant / antifungal / antibacterial effects and processability, availability
For ease, titanium is preferably used.
【００２３】図１は、ＡがチタンＴｉ、Ｍがパラジウム
Ｐｄである場合における本発明の建築材料の金属混合体
の相状態を表すモデル断面図である。表面及びその近傍
にはＴｉＯ2 相１０及びＴｉＰｄ2 相１４が分散してお
り、ＴｉＯ2 相は光触媒機能を発現し、ＴｉＰｄ2 相は
該機能を促進させる。内部にいくに従って、光触媒機能
に係わらないＴｉ相１２が多くなり、Ｔｉ相１２とＴｉ
Ｐｄ2 相１４とが分散した組織になり、これらは連続的
に構成されている。FIG. 1 is a model sectional view showing a phase state of a metal mixture of a building material of the present invention when A is titanium Ti and M is palladium Pd. The TiO 2 phase 10 and the TiPd 2 phase 14 are dispersed on the surface and in the vicinity thereof. The TiO 2 phase expresses a photocatalytic function, and the TiPd 2 phase promotes the function. As going into the interior, the number of Ti phases 12 not related to the photocatalytic function increases, and the Ti phases 12 and Ti
The Pd 2 phase 14 has a dispersed structure, and these are continuously formed.
【００２４】前記の如く、光触媒機能を有する酸化チタ
ン／金属相と、担体となるチタン／金属相は同一の建築
材料組織を構成しているため、光触媒相は担体から剥離
することはなく、実用に耐える強度と耐剥離性を有する
建築材料となる。As described above, since the titanium oxide / metal phase having a photocatalytic function and the titanium / metal phase serving as a carrier constitute the same building material structure, the photocatalyst phase does not peel from the carrier and is practically used. It is a building material having strength and peeling resistance to withstand.
【００２５】次に、本出願に係わる第２の発明である建
築材料の製造方法について説明する。始めに、光触媒活
性を示す金属酸化物を生成せしめる金属及び金属酸化物
の光触媒活性を向上させる第二の金属を含有する金属混
合体を製造し、それを所望の形状に加工したのち、加工
したものを酸化処理して建築材料を製造するものである
が、これを、下記一般式（ＩＩ）によって説明する。Next, a method of manufacturing a building material according to the second invention of the present application will be described. First, a metal mixture containing a metal that produces a metal oxide having photocatalytic activity and a second metal that improves the photocatalytic activity of the metal oxide was produced, processed into a desired shape, and then processed. The building material is produced by oxidizing the material, which will be described by the following general formula (II).
【００２６】ここでは、光触媒活性を示す金属酸化物を
生成せしめる金属がＡ、金属酸化物の光触媒活性を向上
させる第二の金属がＭで表されている。まず、下記一般
式（ＩＩ）で表される金属混合体すなわち合金を製造
し、Here, the metal that forms a metal oxide exhibiting photocatalytic activity is represented by A, and the second metal that improves the photocatalytic activity of the metal oxide is represented by M. First, a metal mixture or alloy represented by the following general formula (II) is produced,
【００２７】[0027]
【化９】一般式（ＩＩ） 〔Ａ〕X 〔ＡＭy 〕1-X 又は〔Ａ〕X Ｍ1-X （式中、ＡはＴｉ Ａｇ Ｃｕ Ｚｎからなる群より選
択される金属を表し、ＭはＰｔ、Ａｕ、Ｐｄ、Ａｇ、Ｃ
ｕ、Ｎｉ、Ｃｏからなる群より選択される金属を表し、
ｘは０．３≦ｘ＜１、ｙは金属Ａと結合する金属Ｍ固有
の整数であって、ｙ＝１、２、３のいずれかを表す。） 該合金を所望の形状に加工したのち、該合金加工体を酸
化処理するものである。[A] X [AM y ] 1-X or [A] X M 1-X (where A represents a metal selected from the group consisting of Ti Ag Cu Zn, M is Pt, Au, Pd, Ag, C
u, Ni, represents a metal selected from the group consisting of Co,
x is 0.3 ≦ x <1, and y is an integer unique to the metal M that binds to the metal A, and represents one of y = 1, 2, and 3. After processing the alloy into a desired shape, the processed alloy is oxidized.
【００２８】前記一般式（ＩＩ）で表される合金は、室
温では「金属Ａからなるα相と金属Ａと金属Ｍの複合体
相」が微細かつ均一に分散した混合組織もしくは「金属
Ａからなるα相と金属Ｍ」が微細かつ均一に分散した混
合組織を呈する。ｘは金属Ａと金属Ｍの複合体相の金属
Ｍに対するモル比もしくは金属Ａの金属Ｍに対するモル
比を表し、ｙは、金属Ａと金属Ｍの複合体相における金
属Ｍの金属Ａに対するモル比を表す。At room temperature, the alloy represented by the general formula (II) has a mixed structure in which the “α phase composed of metal A and the composite phase of metal A and metal M” are finely and uniformly dispersed, or “metal A A mixed phase in which the “α phase and the metal M” are finely and uniformly dispersed. x represents the molar ratio of the composite phase of metal A and metal M to metal M or the molar ratio of metal A to metal M, and y is the molar ratio of metal M to metal A in the composite phase of metal A and metal M. Represents
【００２９】このような混合組織の金属混合体（合金）
を製造し、板や箔等の所望の使用形状に加工したのち、
酸化処理を行う。酸化処理を行う前に、熱処理等の前処
理を施してもよい。前記合金を成型加工したものに表面
洗浄を施し、その後、酸化処理を行うものであるが、処
理の均一性、光触媒相の強度の観点から、酸化処理は電
解質溶液中での陽極酸化処理が好ましい。酸化処理を行
うと、混合組織のうち「金属Ａからなるα相」の表面が
酸化して金属酸化物相を形成させることができる。A metal mixture (alloy) having such a mixed structure
After manufacturing and processing to the desired use shape such as plate and foil,
Perform oxidation treatment. Before performing the oxidation treatment, a pretreatment such as a heat treatment may be performed. The surface of the alloy is subjected to surface cleaning and then oxidized.However, from the viewpoint of the uniformity of the treatment and the strength of the photocatalytic phase, the oxidizing treatment is preferably anodized in an electrolyte solution. . When the oxidation treatment is performed, the surface of the “α phase composed of metal A” in the mixed structure is oxidized to form a metal oxide phase.
【００３０】かくして、光触媒反応における酸化分解反
応の役目を担う酸化チタン等の金属酸化物からなる相
と、還元反応に対する触媒として光触媒反応を促進する
役目を担う金属Ｍからなる相もしくは金属Ｍと金属Ａと
の複合体相とが、合金表面に微細にかつ均一に分散した
リジッドな光触媒相を容易に得ることができる。一般式
（ＩＩ）として、本発明に特に適する金属酸化物を生成
せしめる金属として、金属Ａが例示されているが、本発
明は、これに限定されるものではなく、金属酸化物を生
成せしめる金属としては、例えば、タングステン、鉄、
アルミニウム等も好ましく用いることができ、その他光
触媒機能を発現する金属酸化物を生成せしめる金属であ
れば任意に用いることができるのは、言うまでもない。
以下に、具体例を挙げて本発明をさらに詳細に説明す
る。Thus, a phase composed of a metal oxide such as titanium oxide which plays a role of an oxidative decomposition reaction in a photocatalytic reaction, and a phase composed of a metal M or a metal which plays a role of promoting a photocatalytic reaction as a catalyst for a reduction reaction. A rigid photocatalyst phase in which the composite phase with A is finely and uniformly dispersed on the alloy surface can be easily obtained. In the general formula (II), the metal A is exemplified as a metal that forms a metal oxide particularly suitable for the present invention, but the present invention is not limited to this, and the metal that forms the metal oxide is not limited thereto. As, for example, tungsten, iron,
It is needless to say that aluminum or the like can be preferably used, and any metal can be used as long as it generates a metal oxide exhibiting a photocatalytic function.
Hereinafter, the present invention will be described in more detail with reference to specific examples.
【００３１】（実施例１） チタン−パラジウム二元系
からなる建築材料の製造 図２は、金属混合体 チタン−パラジウム二元系状態図
を示す。(Example 1) Production of a building material composed of a titanium-palladium binary system FIG. 2 shows a phase diagram of a metal mixture titanium-palladium binary system.
【００３２】一般式（ＩＩ）において、ＡがＴｉ、Ｍが
Ｐｄ、ｚが２の場合である。金属混合体（以下、合金と
称する）Ａ、Ｂ及びＣはそれぞれｘ＝０．９、０．８、
０．７の組成で溶製したものである。In the general formula (II), A is Ti, M is Pd, and z is 2. Metal mixtures (hereinafter referred to as alloys) A, B and C are respectively x = 0.9, 0.8,
It was produced with a composition of 0.7.
【００３３】各合金Ａ、Ｂ及びＣの鋳塊を９００℃にお
いて１１０mm幅、２mm厚の板状に熱間圧延し、５重量％
フッ素水溶液中で酸洗いして表面の酸化膜を除去した。
次いで、内装金属タイルとして、１００mm角、１．６mm
厚に切断した。The ingot of each of the alloys A, B and C was hot-rolled at 900 ° C. into a plate having a width of 110 mm and a thickness of 2 mm.
The oxide film on the surface was removed by pickling in a fluorine aqueous solution.
Next, as an interior metal tile, 100 mm square, 1.6 mm
Cut into thick.
【００３４】図３は、陽極酸化処理装置の概略図であ
る。前記各合金は、アノード１６に接続され、カソード
１８には金属アルミニウムが接続される。セル２０中に
は、１重量％リン酸水溶液２２が満たされている。電圧
計２４、電流計２６を観察して、電圧を調整しながら、
直流電力供給装置２８により電力を供給して、陽極酸化
処理を行った。かくして、前記各合金で作製された金属
タイルを、図３に示す陽極酸化処理装置のアノード１６
に取り付けて、１重量％リン酸水溶液中で、電圧１０〜
２５０Ｖで陽極酸化処理を行うことによって、各合金中
のチタン相（α相）を酸化し、表面に数十Å〜数μｍの
厚さの酸化チタン相を形成させ、防臭・防黴・防菌機能
を有する金属タイルを得た。得られた金属タイルの表面
には、一般式（Ｉ）において、ＡがＴｉ、ＭがＰｄ、ｚ
が２の場合であり、ｘがそれぞれ０．９、０．８、０．
７であるような金属混合体が形成されている。FIG. 3 is a schematic diagram of an anodizing apparatus. Each of the alloys is connected to the anode 16 and the cathode 18 is connected to metallic aluminum. The cell 20 is filled with a 1% by weight phosphoric acid aqueous solution 22. Observe the voltmeter 24 and ammeter 26 and adjust the voltage
Anodizing treatment was performed by supplying power from the DC power supply device 28. Thus, the metal tiles made of each of the above alloys were transferred to the anode 16 of the anodizing apparatus shown in FIG.
To a voltage of 10% in a 1% by weight phosphoric acid aqueous solution.
By performing anodizing treatment at 250 V, the titanium phase (α phase) in each alloy is oxidized to form a titanium oxide phase having a thickness of several tens of μm to several μm on the surface, thereby preventing odor, mildew and bacteria. A functional metal tile was obtained. On the surface of the obtained metal tile, in the general formula (I), A is Ti, M is Pd, z
Is 2, and x is 0.9, 0.8, 0.
7 is formed.
【００３５】（実施例２） チタン−銀二元系からなる
建築材料の製造 図４は、金属混合体 チタン−銀二元系状態図を示す。Example 2 Production of Building Material Composed of Titanium-Silver Binary System FIG. 4 shows a phase diagram of a metal mixture titanium-silver binary system.
【００３６】一般式（ＩＩ）において、ＡがＴｉ、Ｍが
Ａｇ、ｚが２の場合である。合金Ｄ及びＥは各々ｘ＝
０．９、ｘ＝０．７の組成で溶製した。In the general formula (II), A is Ti, M is Ag, and z is 2. Alloys D and E each have x =
It was melted with a composition of 0.9 and x = 0.7.
【００３７】各合金Ｄ及びＥの鋳塊を、実施例１と同様
に処理して、防臭・防黴・防菌機能を有する金属タイル
を得た。得られた金属タイルの表面には、一般式（Ｉ）
において、ＡがＴｉ、ＭがＡｇ、ｚが２の場合であり、
ｘがそれぞれ０．９、０．７であるような金属混合体が
形成されている。The ingots of the alloys D and E were treated in the same manner as in Example 1 to obtain metal tiles having deodorant, fungicide and antibacterial functions. The surface of the obtained metal tile has the general formula (I)
In the above, A is Ti, M is Ag, and z is 2.
A metal mixture is formed in which x is 0.9 and 0.7, respectively.
【００３８】（試験例１） 金属タイルの防臭性・耐剥
離性の評価 図５は、防臭性評価試験装置の概略図を示す。(Test Example 1) Evaluation of Deodorization and Peeling Resistance of Metal Tile FIG. 5 is a schematic diagram of a deodorization evaluation test apparatus.
【００３９】防臭性評価試験の方法としては、石英ガラ
ス製実験槽３０底部に、金属タイルの試料３２を設置す
る。石英ガラス製実験槽３０内に、標準ガス発生装置３
４からガス供給口３６を経てアルデヒドガスを供給す
る。装置内には、圧力計３８、攪拌子４０が設置され、
ガスセンサー４２、温湿度計４４、紫外線強度計４６に
より、内部状態を観測することができ、ガスセンサー４
２によってアルデヒドガスの濃度を測定することによっ
て防臭性を評価する。As a method of the evaluation test of the deodorizing property, a sample 32 of a metal tile is placed at the bottom of a laboratory tank 30 made of quartz glass. A standard gas generator 3 is installed in an experimental tank 30 made of quartz glass.
The aldehyde gas is supplied from 4 through a gas supply port 36. In the apparatus, a pressure gauge 38 and a stirrer 40 are installed,
The internal state can be observed by the gas sensor 42, the temperature / humidity meter 44, and the ultraviolet intensity meter 46.
The deodorizing property is evaluated by measuring the concentration of the aldehyde gas according to 2.
【００４０】実施例１及び２で得られた金属タイル試料
３２を、処理面を上にして防臭性評価試験装置の石英ガ
ラス製実験槽３０の底部に設置した。The metal tile sample 32 obtained in each of Examples 1 and 2 was placed on the bottom of a quartz glass test tank 30 of a test device for evaluating deodorization, with the treated surface facing upward.
【００４１】評価装置内にガス供給口３６よりアルデヒ
ド５ppm を導入し、ＢＬランプ（ブラックランプ）（図
示せず）により評価装置の上部より６０分間照射し、そ
のときのアルデヒド濃度の時間的変化を、ガスクロマト
グラフィーにより測定し、アルデヒド残存率の低減の度
合いをもって防臭性能の指標とした。5 ppm of aldehyde was introduced into the evaluation device from the gas supply port 36, and the sample was irradiated with a BL lamp (black lamp) (not shown) for 60 minutes from the upper portion of the evaluation device. The degree of reduction in the residual ratio of aldehyde was used as an index of deodorant performance.
【００４２】比較品として、酸化チタンゾル水溶液をス
ピンコーティング法にて塗布し、金属タイル上に酸化チ
タン−パラジウム薄膜を成膜させたものを試料として、
同様に評価した。As a comparative product, a titanium oxide sol aqueous solution was applied by a spin coating method, and a titanium oxide-palladium thin film was formed on a metal tile as a sample.
It was evaluated similarly.
【００４３】図６は、アルデヒド残存濃度の変化を表す
グラフである。図６において、ａは合金Ａより得られた
金属タイルのアルデヒド残存濃度を示すグラフであり、
以下ｂは合金Ｂ、ｃは合金Ｃ、ｄは合金Ｄ、ｅは合金Ｅ
から得られた金属タイルのアルデヒド残存濃度を示すグ
ラフである。ｆは比較品の金属タイルのアルデヒド残存
濃度を示すグラフである。FIG. 6 is a graph showing a change in the residual aldehyde concentration. In FIG. 6, a is a graph showing the residual aldehyde concentration of the metal tile obtained from alloy A,
Hereinafter, b is alloy B, c is alloy C, d is alloy D, e is alloy E
5 is a graph showing the residual aldehyde concentration of the metal tile obtained from FIG. f is a graph showing the residual aldehyde concentration of the metal tile of the comparative product.
【００４４】図６に示す如く、本発明品、すなわち合金
Ａ、Ｂ、Ｃ、Ｄ、Ｅを酸化処理することにより得られた
金属タイルはいずれも比較品に比べ高い脱臭性能を示し
た。As shown in FIG. 6, the products of the present invention, that is, the metal tiles obtained by oxidizing the alloys A, B, C, D and E all showed higher deodorizing performance than the comparative products.
【００４５】図７は、耐剥離性評価試験方法の概略図を
示す。図７に示すように、金属タイル試料表面中央部
に、カッターナイフを用いて１０mm長さで２ミリ間隔に
疵を付け、５×５のます目を形成した。FIG. 7 is a schematic diagram of a test method for evaluating peel resistance. As shown in FIG. 7, flaws were formed at a center of the surface of the metal tile sample at intervals of 2 mm with a length of 10 mm using a cutter knife to form 5 × 5 squares.
【００４６】次に、粘着テープをます目部分に貼付して
テープのうえから充分こすった後、テープを剥がし、試
験片の切れ目部分を顕微鏡観察して、酸化チタン膜が剥
がれずに残っているます目の数を数えて、剥離強度のパ
ラメーターとした。Next, an adhesive tape was adhered to the squared portion and rubbed sufficiently from above the tape, the tape was peeled off, and the cut portion of the test piece was observed with a microscope, and the titanium oxide film remained without peeling. The number of squares was counted and used as a parameter of the peel strength.
【００４７】比較試料として、５ｃｍ角のガラス板に、
スピンコーティング法により、厚さ１μｍの酸化チタン
膜を成膜させたものを用い、同様の評価を行った。As a comparative sample, a 5 cm square glass plate was
The same evaluation was performed using a titanium oxide film having a thickness of 1 μm formed by a spin coating method.
【００４８】本発明品、すなわち合金Ａ、Ｂ、Ｃ、Ｄ、
Ｅを酸化処理することにより得られた金属タイルはいず
れも酸化チタン膜は剥がれず、結果は２５であった。比
較試料は全て剥がれ、結果は０であった。このように、
本発明により得られたこれらの金属タイルは、耐剥離性
に優れていた。The products of the present invention, ie, alloys A, B, C, D,
In any of the metal tiles obtained by oxidizing E, the titanium oxide film did not peel off, and the result was 25. All the comparative samples were peeled off, and the result was 0. in this way,
These metal tiles obtained by the present invention were excellent in peel resistance.
【００４９】金属酸化物のなかでも、酸化チタンは、そ
の膜厚によって様々な発色が得られること、さらには、
酸化チタン膜厚は、陽極酸化電圧にほぼ比例することが
知られている。このため、本発明の建築材料に酸化チタ
ンを用いる場合、酸化処理における酸化電圧をコントロ
ールすることにより、様々な発色の金属建築材料が得ら
れる。また、表面相と内部相が連続的に構成されている
ため、酸化チタン膜厚に係わらず、優れた表面強度を示
すため、目的に応じた発色の建築材料を酸化電位の調整
によって任意に得ることができ、意匠的にも好ましいも
のである。Among the metal oxides, titanium oxide can produce various colors depending on its film thickness.
It is known that the thickness of titanium oxide is approximately proportional to the anodic oxidation voltage. Therefore, when titanium oxide is used as the building material of the present invention, by controlling the oxidation voltage in the oxidation treatment, metal building materials of various colors can be obtained. In addition, since the surface phase and the internal phase are continuously formed, regardless of the thickness of the titanium oxide film, an excellent surface strength is exhibited, so that a building material having a desired color can be arbitrarily obtained by adjusting the oxidation potential. It is also preferable in terms of design.
【００５０】本発明の建築材料は基材として前記特定の
合金を用いるため、加工性に優れ、任意の形状が容易に
得られる。また、陽極酸化によれば、微細で均一な表面
酸化処理が可能なため、複雑な形状の建築材料も、均一
で、かつ、すぐれた光触媒機能を持つ、すなわち、優れ
た防臭・防黴・防菌機能を有するものとすることができ
る。Since the building material of the present invention uses the above-mentioned specific alloy as a base material, it has excellent workability and can easily obtain an arbitrary shape. In addition, according to the anodic oxidation, fine and uniform surface oxidation treatment is possible, so that building materials having complicated shapes have a uniform and excellent photocatalytic function, that is, excellent odor prevention, antifungal and antifungal properties. It can have a fungal function.
【００５１】本発明の建築材料は、前記の如く金属を任
意の形状に加工して、そのまま用いてもよいし、合金か
ら予め薄膜を製造して酸化処理を行った防臭・防黴・防
菌機能を有する薄膜材料を、各種下地材料に接合させて
用いることもできる。The building material of the present invention may be prepared by processing a metal into an arbitrary shape as described above and using it as it is, or a deodorant / antifungal / antibacterial agent obtained by previously producing a thin film from an alloy and subjecting it to oxidation treatment. A thin film material having a function can be used by being bonded to various base materials.
【００５２】本発明の建築材料の使用方法としては、そ
のまま、金属タイルや、内装材として使用するほか、本
発明の複合構造を有する建築材料の薄板を作製し、既存
の建築材料であるセラミックス、モルタル、硝子、鉄
板、アルミ板等に接合して使用することもできる。この
ように、既存材料の上に接合して用いる方法によれば、
合金使用量の低減が可能となり、優れた防臭・防黴・防
菌機能を有する建築材料を安価に提供できる。As a method of using the building material of the present invention, a thin plate of a building material having a composite structure of the present invention is prepared in addition to a metal tile or an interior material as it is, and a ceramic, which is an existing building material, is used. It can also be used by bonding it to mortar, glass, iron plate, aluminum plate and the like. Thus, according to the method of joining and using on existing materials,
The amount of alloy used can be reduced, and a building material having excellent deodorant, fungicide, and antibacterial functions can be provided at low cost.
【００５３】[0053]
【発明の効果】本発明の建築材料は、材料の均一性が高
く、防臭・防黴・防菌機能に優れ、さらに製造が簡便で
あり、かつ、強度があって、耐久性に優れ、しかも、目
的に応じた形状への加工が容易である。本発明の製造方
法によれば、均一で、防臭・防黴・防菌効果の優れた、
任意の形状の建築材料を簡便に得ることができる。Industrial Applicability The building material of the present invention has high uniformity of the material, is excellent in deodorant, antifungal and antibacterial functions, is easy to manufacture, has strength, is excellent in durability, and It is easy to process into a shape according to the purpose. According to the production method of the present invention, uniform, excellent odor control, antifungal and antibacterial effects,
A building material of any shape can be easily obtained.
【図１】チタン−パラジウム合金より得られた建築材料
内の複合体相を表すモデル断面図である。FIG. 1 is a model sectional view showing a composite phase in a building material obtained from a titanium-palladium alloy.
【図２】金属混合体 チタン−パラジウム二元系状態図
である。FIG. 2 is a binary diagram of a metal mixture titanium-palladium binary system.
【図３】陽極酸化処理装置の概略図である。FIG. 3 is a schematic diagram of an anodizing apparatus.
【図４】金属混合体 チタン−銀二元系状態図である。FIG. 4 is a metal mixture titanium-silver binary system diagram.
【図５】防臭性評価試験装置の概略図である。FIG. 5 is a schematic view of an apparatus for evaluating deodorization properties.
【図６】アルデヒド残存濃度の変化を表すグラフであ
る。FIG. 6 is a graph showing a change in residual aldehyde concentration.
【図７】耐剥離性評価試験方法の概略図である。FIG. 7 is a schematic diagram of a peeling resistance evaluation test method.
１０ 酸化チタン（ＴｉＯ2 ）相 １２ チタン（Ｔｉ）相 １４ チタン−パラジウム混合（ＴｉＰｄ2 ）相10 Titanium oxide (TiO 2) phase 12 Titanium (Ti) phase 14 Titanium - palladium mixed (TiPd 2) Phase
───────────────────────────────────────────────────── フロントページの続き (72)発明者 斉藤 俊夫 東京都江東区南砂２丁目５番14号 株式 会社竹中工務店 技術研究所内 (72)発明者 長谷川 完 東京都江東区南砂２丁目５番14号 株式 会社竹中工務店 技術研究所内 (72)発明者 藤嶋 昭 神奈川県川崎市中原区中丸子710の５ (72)発明者 橋本 和仁 神奈川県横浜市栄区小菅ケ谷町2000番地 10 南小菅ケ谷住宅２棟506号 (56)参考文献 特開 平７−102678（ＪＰ，Ａ (58)調査した分野(Int.Cl.7，ＤＢ名) B01J 21/00 - 38/74 E04C 2/08 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Toshio Saito 2-5-14-1 Minamisuna, Koto-ku, Tokyo Inside Takenaka Corporation Technical Research Institute Co., Ltd. (72) Kan Hasegawa 2-5-1-14 Minamisuna, Koto-ku, Tokyo No. Takenaka Corporation, Technical Research Institute (72) Inventor Akira Fujishima 710-5 Nakamaruko, Nakahara-ku, Kawasaki-shi, Kanagawa Prefecture (56) References JP-A-7-102678 (JP, A (58) Fields investigated (Int. Cl. 7 , DB name)) B01J 21/00-38/74 E04C 2/08
Claims (6)
を示すＴｉＯ 2 又はＺｎＯである金属酸化物及び該金属
酸化物の光触媒活性を向上させる機能を有するＰｔ、Ａ
ｕ、Ｐｄ、Ａｇ、Ｃｕ、Ｎｉ、Ｃｏからなる群より選択
される第二の金属を含有する金属混合体からなり、内部
が実質的に該金属酸化物を構成するものと同種の金属で
あるＴｉ又はＺｎ及び該金属酸化物の光触媒活性を向上
させる該第二の金属を含有する金属混合体からなり、該
表面及びその近傍と内部が連続的に構成されていること
を特徴とする建築材料。1. A metal oxide whose surface and its vicinity are substantially TiO 2 or ZnO exhibiting photocatalytic activity, and Pt, A having a function of improving the photocatalytic activity of the metal oxide.
Select from the group consisting of u, Pd, Ag, Cu, Ni, Co
A second metal of a metal mixture containing, inside what constitutes substantially the metal oxide and the same metal which is
An architectural structure comprising a metal mixture containing Ti or Zn and the second metal for improving the photocatalytic activity of the metal oxide, wherein the surface, its vicinity and the inside are continuously formed. material.
（Ｉ）で表される金属混合体からなり、 ［化１］ 一般式（Ｉ） 〔ＡＯZ 〕X 〔ＡＭy 〕1-X 又は〔ＡＯZ 〕X Ｍ1-X （式中、ＡはＴｉ又はＺｎを表し、ＭはＰｔ、Ａｕ、Ｐ
ｄ、Ａｇ、Ｃｕ、Ｎｉ、Ｃｏからなる群より選択される
金属を表し、ｚは金属Ａと結合する酸素原子の比であっ
て、ｚ≦２を表し、ｘは０．３≦ｘ＜１、ｙは金属Ａと
結合する金属Ｍ固有の整数であって、ｙ＝１、２、３の
いずれかを表す。） 内部が実質的に一般式（ＩＩ）で表される金属混合体か
らなり、 ［化２］ 一般式（ＩＩ） 〔Ａ〕X 〔ＡＭy 〕1-X 又は〔Ａ〕X Ｍ1-X （式中、ＡはＴｉ又はＺｎを表し、ＭはＰｔ、Ａｕ、Ｐ
ｄ、Ａｇ、Ｃｕ、Ｎｉ、Ｃｏからなる群より選択される
金属を表し、ｘは０．３≦ｘ＜１、ｙは金属Ａと結合す
る金属Ｍ固有の整数であって、ｙ＝１、２、３のいずれ
かを表す。） 該表面及びその近傍と内部が連続的に構成されているこ
とを特徴とする請求項１記載の建築材料。2. The surface and its vicinity are substantially composed of a metal mixture represented by the following general formula (I): [Chemical Formula 1] [AO Z ] X [AM y ] 1 -X Or [AO Z ] X M 1-X (where A represents Ti or Zn , and M represents Pt, Au, P
d represents a metal selected from the group consisting of Ag, Cu, Ni, and Co, z represents the ratio of oxygen atoms bonded to the metal A, and represents z ≦ 2, and x represents 0.3 ≦ x <1. , Y is an integer unique to the metal M bonded to the metal A, and represents one of y = 1, 2, and 3. The interior is substantially composed of a metal mixture represented by the general formula (II), and is represented by the following general formula (II): [A] X [AM y ] 1-X or [A] X M 1-X ( Where A represents Ti or Zn , M represents Pt, Au, P
represents a metal selected from the group consisting of d, Ag, Cu, Ni, and Co, x is 0.3 ≦ x <1, y is an integer specific to metal M bonded to metal A, and y = 1, Represents any of 2,3. 2. The building material according to claim 1, wherein the surface, the vicinity thereof, and the inside are continuously formed.
される金属混合体からなり、 〔ＴｉＯ2 〕X 〔ＴｉＭy 〕1-X 又は〔ＴｉＯ2〕X Ｍ1-X （式中、ＭはＰｔ、Ａｕ、Ｐｄ、Ａｇ、Ｃｕ、Ｎｉ、Ｃ
ｏからなる群より選択される金属を表し、ｘは０．３≦
ｘ＜１、ｙはＴｉと結合する金属Ｍ固有の整数であっ
て、ｙ＝１、２、３のいずれかを表す。） 内部が実質的に下記式で表される金属混合体からなり、 〔Ｔｉ〕X 〔ＴｉＭy 〕1-X 又は〔Ｔｉ〕X Ｍ1-X （式中、ＭはＰｔ、Ａｕ、Ｐｄ、Ａｇ、Ｃｕ、Ｎｉ、Ｃ
ｏからなる群より選択される金属を表し、ｘは０．３≦
ｘ＜１、ｙは金属Ｔｉと結合する金属Ｍ固有の整数であ
って、ｙ＝１、２、３のいずれかを表す。） 該表面及びその近傍と内部が連続的に構成されているこ
とを特徴とする建築材料。3. A made from the surface and the metal mixture in which the vicinity thereof are substantially represented by the following formula, [TiO 2] X [TiM y] 1-X or [TiO 2] X M 1-X (wherein , M are Pt, Au, Pd, Ag, Cu, Ni, C
x represents a metal selected from the group consisting of
x <1, y is an integer peculiar to the metal M bonded to Ti, and represents one of y = 1, 2, and 3. ) Internally substantially a metal mixture which is expressed by the following equation, in [Ti] X [TiM y] 1-X or [Ti] X M 1-X (wherein, M is Pt, Au, Pd, Ag, Cu, Ni, C
x represents a metal selected from the group consisting of
x <1, y is an integer peculiar to the metal M bonded to the metal Ti, and represents one of y = 1, 2, and 3. A building material characterized in that the surface, its vicinity and the inside are continuously formed.
める金属であるＴｉ又はＺｎ及び金属酸化物の光触媒活
性を向上させる機能を有するＰｔ、Ａｕ、Ｐｄ、Ａｇ、
Ｃｕ、Ｎｉ、Ｃｏからなる群より選択される第二の金属
を含有する金属混合体を製造し、 該金属混合体を所望の形状に加工したのち、 該金属混合体を加工したものを酸化処理して表面に光触
媒相を形成することを特徴とする建築材料の製造方法。4. Pt, Au, Pd, Ag, which has a function of improving the photocatalytic activity of a metal such as Ti or Zn , which generates a metal oxide exhibiting photocatalytic activity, and a metal oxide .
Producing a metal mixture containing a second metal selected from the group consisting of Cu, Ni, and Co , processing the metal mixture into a desired shape, and then subjecting the processed metal mixture to an oxidation treatment And touch the surface
A method for producing a building material, comprising forming a medium phase .
製造し、 ［化３］ 一般式（ＩＩ） 〔Ａ〕X 〔ＡＭy 〕1-X 又は〔Ａ〕X Ｍ1-X （式中、ＡはＴｉ又はＺｎを表し、ＭはＰｔ、Ａｕ、Ｐ
ｄ、Ａｇ、Ｃｕ、Ｎｉ、Ｃｏからなる群より選択される
金属を表し、ｘは０．３≦ｘ＜１、ｙは金属Ａと結合す
る金属Ｍ固有の整数であって、ｙ＝１、２、３のいずれ
かを表す。） 該金属混合体を所望の形状に加工したのち、 該金属混合体を加工したものを酸化処理して表面に光触
媒相を形成することを特徴とする請求項４記載の建築材
料の製造方法。5. A metal mixture represented by the following general formula (II) is produced: [Chemical Formula 3] [A] X [AM y ] 1-X or [A] X M 1-X ( Where A represents Ti or Zn , M represents Pt, Au, P
represents a metal selected from the group consisting of d, Ag, Cu, Ni, and Co, where x is 0.3 ≦ x <1, y is an integer specific to metal M bonded to metal A, and y = 1, Represents any of 2 and 3. After processing the metal mixture into a desired shape, the processed metal mixture is oxidized and the surface is illuminated.
The method for producing a building material according to claim 4 , wherein a medium phase is formed .
ｏからなる群より選択される金属を表し、ｘは０．３≦
ｘ＜１、ｙは金属Ｔｉと結合する金属Ｍ固有の整数であ
って、ｙ＝１、２、３のいずれかを表す。） 該金属混合体を所望の形状に加工したのち、 該金属混合体を加工したものを酸化処理して表面に光触
媒相を形成することを特徴とする請求項４記載の建築材
料の製造方法。6. A manufacturing metal mixture which is expressed by the following formula, [Ti] X [TiM y] 1-X or [Ti] X M 1-X (wherein, M is Pt, Au, Pd, Ag, Cu, Ni, C
x represents a metal selected from the group consisting of
x <1, y is an integer peculiar to the metal M bonded to the metal Ti, and represents one of y = 1, 2, and 3. After processing the metal mixture into a desired shape, the processed metal mixture is oxidized and the surface is illuminated.
The method for producing a building material according to claim 4 , wherein a medium phase is formed .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23956393A JP3316048B2 (en) | 1992-11-06 | 1993-09-27 | Building material and manufacturing method thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4-297395 | 1992-11-06 | ||
| JP29739592 | 1992-11-06 | ||
| JP23956393A JP3316048B2 (en) | 1992-11-06 | 1993-09-27 | Building material and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06198196A JPH06198196A (en) | 1994-07-19 |
| JP3316048B2 true JP3316048B2 (en) | 2002-08-19 |
Family
ID=26534312
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23956393A Expired - Fee Related JP3316048B2 (en) | 1992-11-06 | 1993-09-27 | Building material and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3316048B2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2186733T3 (en) * | 1994-11-16 | 2003-05-16 | Toto Ltd | FUNCTIONAL PHOTOCATALITICAL MATERIAL AND METHOD TO PRODUCE IT. |
| AU718733B2 (en) * | 1995-03-20 | 2000-04-20 | Toto Ltd. | Method for photocatalytically rendering a surface of a substrate superhydrophilic, a substrate with a superhydrophilic photocatalytic surface, and method of making thereof |
| JP3972080B2 (en) * | 1995-07-08 | 2007-09-05 | Ｔｏｔｏ株式会社 | Automobile and its painting method |
| JP3339304B2 (en) * | 1995-12-22 | 2002-10-28 | 東陶機器株式会社 | Painted object and painting method |
| JPH11197516A (en) * | 1998-01-09 | 1999-07-27 | Takenaka Komuten Co Ltd | Photocatalyst material and its production |
| JP4864111B2 (en) * | 2009-04-06 | 2012-02-01 | 富士通株式会社 | Method for producing photocatalyst composite material |
| JP2015131282A (en) * | 2014-01-15 | 2015-07-23 | 昭和電工株式会社 | Photocatalyst, coating agent and interior material |
| JP6403330B2 (en) * | 2015-01-21 | 2018-10-10 | 学校法人 関西大学 | Organic synthesis method using alloying element in active metal oxide film as heterogeneous catalyst |
-
1993
- 1993-09-27 JP JP23956393A patent/JP3316048B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| 特開 平７−１０２６７８（ＪＰ，Ａ |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06198196A (en) | 1994-07-19 |
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